Process of forming chemical reaction products of metal oxides



R. PYZEL PROCESS 0F' FORMING CHEMICAL REACTION PRODUCTS OF METAL OXIDES Filed Aug. 19, 1944 L ww.

N A NN am ww n u QN L YT [N V EN TOR. /faf-Ar /Drzfz BY 9,

Q7 65%,@ T'OR/VEYJ May l0, 1949.

Patented May 10, 1949 PROCESS OF FORM] NG CHEBIICAL REAC- TION PRODUCTS OF METAL OXmES Robert Pyzel, New York, N. Y., asignar to The M. W. Kellogg Company, corporation of Delaware Jersey City, N. J., a

Application August 19, 1944, Serial No. 550,298

(Cl. B-100) Claims.

This invention relates to an improved method for producingcompounds of oxides of metals of group II of the periodic system with at least one oxide of a metal of groups III and IV. More particularly the invention relates to an improved method of reacting oxides of metals of group II with oxides of metals of groups III and IV. Still more particularly the invention relates to an improved process for reacting alkaline earths, such as calcium oxide and magnesium oxide with oxides of metals of groups III and IV, such as alumina and silica. Still more particularly, the invention relates to an improved method ior reacting alkaline earths with silica and alumina to produce hydraulic cements.

The compounds produced in accordance with the improved process include primarily the silicates and aluminates oi alkaline earth metals, which are hydraulic. The production of such hydraulic compounds represents the most important application of the improved process. The process will, therefore, be described particularly byreference to the production o! hydraulic cements, as exemplified by Portland cement. It will be understood. however, that the reference to the production of Portland cement in the further description of the invention merely exemplies an important application of an improved method which is capable of other embodiments, as will be apparent to those skilled in the art.

The most important constituent oi' Portland cement is calcium silicate which is present in the usual commercial product in the form of tricalcium silicate and also in the form of dicalcium silicate. ot Portland cement is tri-calcium aluminate, which is thought to impart setting properties to the cement.

Portland cement is made ordinarily from any raw materials which provide CaO, SiO: and A1203 in the desired proportions. In certain uses of Portlandcement iron oxide is considered as a valuable ingredient, as is magnesia. Iron oxidey serves somewhat as a replacement for A1203 but also imparts its own peculiar properties to the cement. Magnesia likewise :may replace CaO in part but also imparts its own characteristic properties to the cement.

In the United States the princip l raw material employed in the manufacture i Portland cement is cement rock which is an argillaeeous limestone containing CaO, S102 and A1203 in almost the proportions ordinarily desired in Portland cement. Small amounts oi lime or clay may be added to make any necessary adjustment oi' Another important ingredient the proportion oi' these oides in the raw material. Another important raw material which is employed in the United States is marl which is' an impure calcium carbonate containing clay and magnesia. This also is used in combination with clays or limestone to produce the desired proportions of the essential ingredients for the Portland cement. It is to be understood, however, that Portland cement may be produced from any raw materials containing the CaO, SiO: and A: which are regarded as the essential constituents of Portland cement. In previous commercial operations the raw materials are flnely ground and burned in a rotary kiln into which they are introduced either as a powder or as a slurry. 'I'he raw materials are burned in the rotary kiln in the well-known manner and emerge as clinker which is then ground to produce the cement produce.

It is an object oi' this invention to provide an improved process for treating the raw materials ordinarily employed in the production oi hydraulic cement which requires a substantially lower expenditure of fuel than previous methods and which produces a cement product of greater uniformity than the product oi' previous processes. It is the general object of the invention to provide an improved process for reacting oxides of metals of group II, particularly alkaline earths, with oxides oi' metals of groups III and IV, such as silica and alumina, under conditions requiring the expenditure oi' a minimum amount oi' fuel and which facilitate the formation of a highly uniform product. Other objects and advantages of the invention will be apparent from the following description.

In accordance with the improved process oi' this invention the raw materials are formed into a ne powder, which may be finer than the powder previously employed in the rotary kiln method, and the powder is subjected to reaction conditions in a, reactor while being maintained in a relatively dense pseudo-liquid condition in the reactor by the passage oi a. gas upwardly through the powder mass at the proper velocity. The powdered raw material may be charged to the reactor in the chemical form in which it is customarily charged to a rotary kiln or the powdered raw material may be subjected to a. preliminary burning in a separate zone to convert vthe calcium carbonate to calcium oxide.

The heat necessary to sustain the reaction may be supplied with the stream oi' gas, or fuel may be introduced directly into the iluidlzed powdered mass and burned therein to provide the necessary heat. It is more economical of aisance heat and conducive to the preparation of a uniform product to subject the raw material to a preliminary treatment in a separate chamber to convert the calcium carbonate to calcium oxide. It is characteristic of this invention that the reaction zone is maintained at a substantially uniform temperature throughout as a result of the circulation of the powdered particles throughout the iluidized mass of reactants. Consequently it is preferable to convert the calcium carbonate to calcium oxide in a separate preliminary treatment since this operation is best carried out at a temperature considerably lower than the temperature necessary for reacting the calcium oxide with silica and alumina to produce the hydraulic product. While such separate preliminary treatment is necessary only for that portion of the raw material containing calcium carbonate it will be found convenient ordinarily to subject the whole raw material to such preliminary treatment, since calcium carbonate ordinarily comprises the h greater part of the raw material.

In accordance with the improved process the finely divided raw material. which may or may not have been treated previously to convert the carbonate to the oxide. is suspended in the reactor in an upwardly flowing gas stream as a dense. pseudo-liquid turbulent mass in which the powder particles circulate at a high rate to produce intimate mixing of the mass of reactants. The

gas stream is passed upwardly through the mass at a velocity which is sufllcient to maintain the reactants substantially in suspension in the gas stream. The velocity of the gas stream is maintained suflloiently low to maintain the greater part of the mass of reactants in a pseudo-liquid condition in which it exhibits many of the properties of a true liquid, particularly as to dowability and density. At the same time the velocity is maintained sufliciently high to produce in the relatively dense pseudo-liquid mass of ilnely divided reactants a highly turbulent motion of the particles whereby they circulate at a high rate throughout the pseudo-liquid mass.

The iluidized mass of reactants is quite dense, resembling in this respect a settled mass oi' the same material. The density of the fluldized mass may be not less than half that of the settled mass. While the dense turbulent reactant mass is said to be suspended in the gas stream this does not imply vany movement of the mass as a whole along the path of ilow of the gas stream. The mass of finely divided reactants is suspended in the gas stream but not entrained therein, although a portion of the suspended solid may be carried away from the dense fluidized mass by becoming entrained in the gas stream emerging from the dense pseudo-liquid mass.

The gas mixture is introduced into the reactor through an inlet in the bottom thereof whereby the gas stream upwardly through the mass of reactants to be maintained in a uidized condition. Conveniently the inlet comprises one or more connections whose aggregate cross-sectional area is wsubstantially less than the corresponding dimension of the space in which the iiuidized mass of reactants is to be maintained. The gas stream thus into the reactor at a relatively high velocity which prevents the passage of solids out of the reactor against the entering gas stream. Inside the reactor the velocity of the gas stream decreases to the rate necessary to produce the desired degreec'f iluidization of the mass of reactants. For convenience the velocity ofthe gasstreaminthe reactorisgiveninterms of the theoretical velocity of the gas stream through an empty reactor and referred to hereafter as the superilcial velocity. It is evident, however, that the velocity of the gas stream decreases to the superficial velocity only if the reactor is suiilciently larger than the volume of nuidiaed reactants to permit the maximum possible disengagement of the gas stream and the suspended solids. As the concentration of finely divided solids in the fluidized mass varies from a maximum at the bottom to a minimum at the top the linear velocity of the gas stream would normally decrease as it passes upwardly through the nuidized mass, in the absence of reaction. The extent of the variation in the density oi. the fiuidized mass in the reactor is affected by the supercial velocity, the greatest variation in the density of the mass being observed at relatively high superficial velocity. The linear velocity of the gas stream may be affected also bythe change in volume of the gas stream, as it passes up through the reactor, as a result of an increase in temperature of the gas stream and as a result of the formation of gases by the reaction.

I1' the reactor is somewhat larger than the volume occupied by the fiuidized mass of solid reactants the solids in the reactor appear to be distributed in two visually distinct phases. The first of these is the relatively dense, pseudo-liquid mass of uidized nnely divided reactants, previously described, which occupies the lower portion of the reactor and comprises all but a minor prpportion of the solids in the reactor. This phase is designated as the dense phase. The second phase, which occupies the upper part of the reactor, is a diffuse phase in which the concentration of solids is far less, and of a different order of magnitude, than the average concentration in the dense phase. The diffuse phase may be said to be a disengaging zone in winch the solids lifted above the dense phase by the gas stream are disengaged therefrom to the extent that such solids are present in excess of the carrying capacity of the gas stream at the minimum velocity reached by the gas stream in the reactor. Between the dense phase of high concentration and the diiluse phase of low concentration there is a relatively narrow zone in which the the concentration of solids changes in a short space from the high concentration of the dense phase to the low concentration of the diiluse phase. This zone has the appearance of an interface between two visually distinct phases.

While the invention includes within its scope the use of reactants of a sutliciently large particle size such that substantially no part of the reactants is carried by entrainment in the gas stream at the maximum superilcial velocity, the preferred method of operation involves ordinarily the use of nnely divided reactants and operating conditions such that a portion of the reactants is carried by entrainment in the gas stream at the supercial velocity. This results from the fact that finely divided reactants are desirable as presenting a greater ratio of surface to volume and, thus aording the maximum eiiiciency of reaction and maximum heat transfer between particles, and from the further fact that sumcient nixing of the mass of finely divided reactants ordinarily requires the use of superilcial velocities which entrain a portion of the nely divided solids in the gas stream. In this preferred method of operation mere settling is not sufficient to disengage ali the solids from the gas stream emerging from the dense phase in the reactor. Hence it may be necessary to provide means to separate entrained solids from the gas stream emerging from the reactor.

The gas stream is Withdrawn from the top of the reactor through an exit which is ordinarily of substantially smaller cross-sectional area than the reactor. This provides a high velocity outlet for the gas which is surrounded by an area in which the gas velocity accelerates. The nearer this zone oi' accelerating gas velocity is to the dense phase the greater is the concentration of solids in the gas stream entering the zone and the greater is the quantity of solids which is carried out of the reactor in the exit gas stream. This quantity approaches the carrying capacity of the high velocity exit gas stream when it is desired to maintain the upper level of the dense phase in the vicinity of the zone of accelerating velocity. In the preferred method of operation, however, the reactor is made sufficiently larger than the required volume of the dense fluidized mass of solids to provide a relatively large diffuse phase in which substantial disengagement of solids from the gas stream occurs by mere settlillg.

The operation is initiated by charging the reactor With a quantity of finely divided solid reactants which it is expected will be equivalent to the mas of solids maintained in the reactor in the dense phase. Thereafter the passage of the gas stream into the reactor and upwardly through the mass of solids is initiated at the velocity which luidizes the mass, i. e., converts it to the relatively dense pseudo-liquid condition involving highly turbulent motion of the particles. Alternatively the highly turbulent pseudo-liquid phase may be established in the reactor initially by iiowing the gas stream through a substantially charging the finely divided solid reactants into the reactor at a rate greater than the carrying capacity of the gas stream at the superficial velocity imposed by the dimensions of the reactor. As a result of this excess loading When the height of the dense phase in the reactor reaches the desired level the introduction of reactants into the reactor is carried on at a reduced rate or is stopped, in accordance with the desired method of operation.

If the reactants charged to the reactor are substantially free of carbonates, whereby there is no necessity for conversion of carbonates to oxdes in the reactor, the net heat effect of the desired reactants is exothermic. In that case it is necessary only to heat the reaction mass to a temperature at which reaction is initiated. Thereafter the heat of reaction must be absorbed to avoid overheating the mass of reactants. The heat of reaction may -be absorbed by the gas stream and the solid reactants, which may be introduced into the reactor at temperatures substantially lower than the reaction temperature level and which are necessarily withdrawn from the reactor at approximately the reaction temperature level. It is a feature of the improved method offoperation that the reaction mass is maintained substantially at a uniform temperature regardless of the heating and cooling means applied to it and regardless of the introduction and withdrawal of solid reactants and gas. It is necessary only to balance the heat absorption by these means against the exothermic heat of reaction and anysupplementary heating means to oxide in the mass by oxygen contained in maintain the entire iiuidized mass of reactants at a desired uniform reaction temperature level.

If the reactants charged to the reactor contain a substantial proportion of carbonates, whereby it is necessary to convert such carbonates to reactor with the evolution of carbon dioxide the net heat eii'ect of the reactions may be endothermic. In that case it is necessary continuously to supply substantial heat to the reactor to maintain the fluidized mass of reactants at the desired reaction temperature level. To supply heat to the reaction, or to eii'ect the preliminary heating of the reaction mass to the reaction temperature, any suitable heating means may be employed. Conveniently fuel may be injected directly into the reactor and burned by means of oxygen in the gas stream. Such fuel may be in the form of a combustible gas, such as natural gas, a combustible liquid, such as petroleum oil, or finely divided solids, such as coal or coke. Alternatively combustion may be carried out in a separate chamber from which the hot gases pass into the reactor to effect simultaneous aeration and .heating of the mass. The use of finely divided solids, injected directly into the reactor, is an efficient heating means in operations in which the ash resulting in such combustion can be tolerated in the product. For example, finely the high circulation rate ofthe particles thereof and is burned uniformly throughout the fluidized the gas stream employed for effecting uidization. In this manner uniform heating of the mass is effected.

The use of the gas stream to eect combustion as well as to effect aeration introduces another factor to govern the volume of such gas introduced into the reactor. To produce the required amount of heating it may be necessary to employ a quantity of gas, such as air, in excess of the minimum amount necessary to effect iiuidization, in order to supply suiiicient oxygen for combustion in the reactor.

The mass of reactants may be maintained in replaced with fresh reactants. Preferably, however, a small propor-` tion of the uidized mass of reactants is withdrawn continuously from the reactor and continuously replaced with fresh reactants. This proportion is regulated to provide an average residence time suiicient to effect complete reaction whereby the material continuously withdrawn from the reactor consists substantially completely of the desired reaction product.

In accordance with a preferred modification of the invention raw materials comprising substantial proportions of carbonates are treated in two reaction stages. In this method of operation the reactants are introduced into a rst stage, maintained under the above described iiuidized conditions, in which the temperature is maintained at the level necessary to convert the carbonates to oxides. Since this reaction is highly endothermic it is necessary to supply a substantial quantity of fuel continuously to this stage. The product of this operation then passes to a second treating stage, corresponding to the reaction zone described above.V in which the iiuidized mass is maintained at the temperature necessary to form the desired cement product. As the reactions occurring in this stage are exothermic it is necessary to supply only a relatively small amount of heat to the reaction mass. The heat of reaction is absorbed in heating the entering reactants and gas stream.

To produce the turbulent pseudo-liquid condition in the dense phase it is desirable that at least a substantial proportion of the mass oi reactants shall consist of particles whose free settling rate is less than the superciai velocity in the reactor, whereby such particles are capable of being entrained in the gas stream. The mass of reactants may consist advantageously of a mixture of particles varying in sine from to 400 microns (average diameter). However. particles of smaller corresponding feet per second. depending upon the degree of turbulence desired and on the necessity for extra oxygen for combustion purposes to maintain a highly nuidized mass of solids at a uniform temperature. A minimum superficial velocity of approximately 0.5 foot per second is necessary for most purposes and velocities between that gure and 1.5 feet per second will be found useful.

The gas employed for iluldization may be any gas which does not contain ingredients which eiect undesired reactions in the reactor. Ordinarily air is highly satisfactory as it is substantialiy non-reactive with the reactants and contains oxygen which may be used to support any desired combustion in the reactor. It is evident, however, that any suitable gas may be employed.

The invention includes within its scope a process arrangement for handling the raw material and the product in a manner which is most economical oi' heat. This may include the provision of heat exchangers such as chambers in which the reactants are maintained in the finely divided iluidized condition and through which the finely divided solids now in a continuous or semicontinuous manner. This arrangement, and the improved process in general. will be described further and in more detail by reference to the accompanying drawing which is a diagrammatic representation of apparatus for carrying out one modiiiaction of the improved process.

Referring to the drawing a main reactor I is provided for carrying out the treatment of a fluidized raw material substantially iree of carbonates in the manner generally described above. A preliminary carbonate reactor 2 is provided for effecting a preliminary conversion of carbonates to oxides in the manner generally described above. A preheater l is provided for preheating the raw material charged to the carbonate reactor by contact with waste gases from the latter. An economiser I is provided to preheat the gas stream charged to the main reactor, or to the carbonate reactor. by contact thereof with the hot product of the process. 1n the specific modiilcation of the invention illustrated by the drawing preheater I and economiser l are operated in a manner to maintain the reactants or product in a fiuldized condition. It will be understood, however, that this is not necessary in accomplishing the functions of these parts of the process and that any equivalent heat saving means may be stream from carbonate reactor 2 passes through line l to the bottom of preheater f necessary to efl'ect 3. The nnely divided raw material, which may cement rock and clay or limestone, heater 3 by any suitable method. The nnely divided reaction mass may be charged directly into preheater 3 through 4a suitable opening (not lshown prior to initiating the passage of the gas stream therethrough or preheater 3 may be charged with reactants through line l which connects line l with a suitable supply source. The iinely divided reactants are supplied through line B tothegasstreamspassingthroughlinelatthe rate at which such solids can be carried by the gas stream upwardly into preheater I. In this manner the formation of the dense fiuidized mass is enected. When a sumcient volume of the dense in preheater 3 the rate of charging of fresh ieed through line I is ad- ,iusted to correspond to the rate at which it is desired to transfer preheated raw material from preheater 3 to carbonate reactor 2.

The finely divided reactants are introduced through line I by any suitable means but preferably in the form of a mass which is maintained in a iiuidized condition. To assist in maintaining this condition an aerating gas may be introduced into line B through line 1. This aerating gas may be any suitable gas such as air or waste gas or steam and may pass either upwardly in line 3 or downwardly therein or in both directions. A valve l is provided in line l to regulate the rate at which solids are introduced into line i from line 6. The section of line l between line i and preheater 3 may be enlarged in accordance with the increased volume resulting from the addition of solids and to obtain reduced velocity of the gas stream which may be desirable ai'ter the introduction of solids therein.

In preheater 3 the waste gas and the mass oi raw materials is brought to a substantially uniform temperature by permitting a suicient residence time oi the solids in preheater 3. The preheated raw material may be withdrawn from preheater 3 in any suitable manner and from any point thereof for transfer to carbonate reactor 2. Conveniently, however, this is eilected by means of a vertical standpipe i which extends upwardly into preheater 3 to a height substantially below the interface at i0. Standpipe l connects at its lower end with line il through which hot gases from reactor i yand economizer 4 are passed into the lower part oi carbonate re'- actor 2. 'I'he iiuidized preheated raw materials flow into the upper end of standpipe s and pass downwardly therethrough into line Il. The now of such solids through standpipe l may be regulated and assisted by means oi' aerating gases introduced through line il. A valve i3 is provided in standpipe 9 to regulate the now oi solids into line Il. Line il is suitably 'enlarged between standpipe 9 and carbonate reactor 2.

The hot gases passing through line Il will further preheat the raw material to the temperature conversion of carbonates to oxide and may supply a part oi' the endothermic heat of reaction. The remainder oi the heat of reaction is supplied by the introduction of fuel or by other heating means in accordance with the general methods described above. The introduction of fuel directly into carbonate reactor 2 by a pipe line or by a screw conveyer or `by any other means is indicated diagrammatically at Il. The volume o! gas introduced into carbonate reactor 2 through line li ordinarily is somewhat greater than the minimum necessary to effect fluidization of the mass of reactants therein since it is necessary ordinarily to supply additional oxygen to support combustion of the fuel supplied at I4. In any case the mass of reactants in carbonate reactor 2 is maintained in a highly turbulent condition in which the heat exchange between the various parts of the turbulent mass is highly efficient whereby the mass ls substantially at a uniform temperature.l The hot gases pass l from the top of carbonate reactor 2 through line 5 which connects with the bottom of preheater 3 in which the waste gases are contacted with incoming fresh feed as a heat saving measure.

A standpipe I5, similar in operation to'standpipe 9, is provided to withdraw reactants from carbonate reactor 2. The rate of withdrawal of reactants through standpipe I5 is adjusted to maintain an average residence time oi the reactants in the carbonate reactor 2 substantially greater than the time necessary to effect the reaction. As a result the product withdrawn through standpipe I5 for transfer to main reactor I is substantially free of carbonatos. The rate of withdrawal of reactants through standpipe I5 is adjusted also to maintain an interface IB about half Way up in carbonate reactor 2. This permits substantial disengagement of solids from the gas stream prior to passage of the latter to line 5. Fluidizing gases are introduced into standpipe I5 at I1 and a valve I3 is provided to regulate the flow of reactants.

The lower end of standpipe IE connects with line I9 which extends from the top of economizer I to the bottom of the main reactor I. Through line I9 there is introduced into reactor l the gas stream necessary to Iluidize the mass of reactants. This gas stream and the reactants introduced therein from standpipe I5 are at temperatures substantially lower than the reaction temperature level desired in reactor I. However, the gas stream and accompanying reactants entering reactor I from line I9 are preheated to the desired reaction temperature by the highly turbulent iluidizcd mass of reactants in reactor I. which is maintained at the desired reaction temperature level by the exothermic heat of reaction and by a small quantity of fue] introduced through line Ida in a manner similar to the supply of fuel to the carbonate reactor as described above. 'I'he exothermic heat of reaction and the requirements of the process as to volume of uidlz'ing gas and quantity of reactants charged are such that ordinarily the entire heat of reaction is absorbed by the reactants and fluldizing gas introduced from line I9 into reactor I. y

The reaction product is withdrawn continuously from reactor I through a standpipe 29, the rate of withdrawal being adjusted to maintain the interface at the desired level and to provide a holding time of reactants in reactor I substantially greater than the time necessary to eifect the reaction. The hot gases from reactor I pass through line I I to carbonate reactor 2. Line I I als@ receives a part of the gases emerging from economizer L This serves to reduce the temperature of the gas from reactor I to a level more suitable for transmission to reactor 2 and also to supply the extra oxygen necessary to support combustion in reactor 2.

Standpipe 29, which is provided with aerating means at 2| and a valve 22, connects at its lower end with line 23 through which air for the process is introduced into the bottom of economizer 4. A compressor 2l is provided in line 23 to impose the necessary pressure on the system. The

hot product passes downwardly through standpipe 29 into line 23 where it is picked up by the air stream and carried into economizer 4. In economizer I the iiuidlzed mass of the product is maintained to permit effective contact between the air and product. The quantity of air introduced into the system through line 23 is regulated by the requirements of carbonate reactor 2 and reactor I. Since this requires a quantity of air which is greater than the amount necessary to iluidize the reactants in reactor I the preheated air emerging fromthe top of economizer 4 is divided between line I9 which passes to the bottom of reactor I and line 25 which connects with line Il.

The partially cooled product is withdrawn from economizer l in a uidized condition through standpipe 26 which is provided with aerating means 21 and a valve 2B. This product may, if

desired, be passed to a second economizer or other heat saving means. f

The waste gas which passes from the system through line 29`at the top of preheater 3 may be treated for the recovery of solids entrained therein. Suitably this gas is passed through separatory means such as cyclone separators and the solids thus separated are returned to preheater 3. Conveniently such separating means may be placed within preheater 3 and the upper portion thereof in the manner shown diagrammatically in the drawing. A plurality of cyclone separators 39 may be maintained in series, or in parallel, in the upper portion of preheater 3. In the arrangement shown the cyclones are connected by lines 3I to a common header 32 which communicates with line 29. The gas in the upper part of preheater 3 passes into the inlets 33 of cyclones 39, deposits all or a substantial proportion of the entrained solids therein and passes out of the system through lines 3| and 29. The separated solids pass from cyclones 39 through lines 3l to a header 35 from which the returned solids pass downwardly through line 36 to a point substantially below interface ID. A shield 31 may be placed around the lower end of line 33 to minimize the passage of gases into the open end of line 36.

The provision of solids recovery means in cornbination with preheater 3 is advantageous in that it minimizes for the whole system the loss of solids. Furthermore, preheater 3 represents the only place in the system in which the gas temperature is sufllciently low to make practicable 4the application of recovery means. such as` cyclones. Ordinarily this requires that the temperature be not substantially higher than 1000 F.

The solids which are carried out oi reactors I and 2 and economizer 4 by entrainment in the gas streams passing overhead are recovered in the succeeding chamber to which the exit gas stream passes. Thus solids carried overhead by entrainment through line 5 are recovered in preheater 3 and returned to reactor 2 through standpipe 9. Also solids entrained in the gas stream in line I i are recovered in reactor 2 and returned to reactor I through standpipe I5. In a similar manner solids carried overhead from economizer I through lines I9 and 25 are recovered in reactor I and in reactor 2 and returned through standpipes 20 and I5 respectively.

The pressure on the system need be no higher than the pressure necessary to pass the gas stream through the system plus the pressure necessary at 29 to dispose o f the waste gas. The pressure at which the air is supplied through line 2l may be in the order o! 37 pounds gage which is suiiioient to timeline the solids in the four chambers, pass solids through the system and pass the waste gas out through line 20 at a pressure somewhat above atmospheric.

The temperature in main reactor I is maintained at a substantially uniform level within the range oi 2,000-2,650 F. In accordance with a preferred modiilcation of this invention the main reactor is maintained at a temperature below the temperature at which fusion oi, the solids would occur or in the range of 2,000-2,450 l". The maximum temperature permissible without substantial fusion is most desirable.

The temperature in carbonate reactor 2 is maintained at the level necessary to effect rapid conversion ot the carbonates suchFJars calcium carbonate to corresponding oxides. this purpose a temperature of approximately 1650 F. is satisfactory although somewhat lower temperatures may be employed.

The temperatures in preheater 3 and econominer I have no bearing on the reaction and are governed entirely by considerations of emciency in heat saving. Examples oi such temperatures will be given in the following example.

An example of the operation of the process described above will be`given in the following deseription o! the operation oi a plant designed and operated to produce 735 tons per day oi' s Portland cement comprising a mixture oi! dieaicium silicate. tricalcium silicate, tri-calcium aluminate and small amounts o! iron oxide, magnesia and other minor ingredients. This material is produced from a raw material consisting essentially of silica, alumina and calcium carbonate and ground sufiiciently ne that 90% or the powder will pass through a number 1000 sieve. Analysis o! this powder is as follows:

Weight Vper cent This powder has a specinc heat, in the range ot 604,650 F. of about 0.25 B. t. u. per "F. per pound and has a nlling weight o! 50 pounds per cubic ioot.

The above described feed powder is charged to the system at a temperature of about 60" F.

through line 6 at the rate oi 95,000 pounds per hour. At the same time 107,000 pounds per hour o! gas at 1,650 F. is passed through line 5 into preheater I. The inside diameter of line l between line and preheater I is dimensioned with respect to the volume oi gas passing therethrough to provide a linear velocity in that part of line l of approximately 50 feet per second. The resulting dense bed of charged material in the preheater I is thus heated to a temperature of about 050 l'. and the waste gas is withdrawn through line at about the same temperature. heater I has an inside diameter oi' approximately ieet and the dense phase maintained therein occupies about haii' the volume oi' that chamber or about '1,360 cubic feet. The gas iiow corre- Ple- 70 pounds per hour. This-air. which is at a temabout 1.5 feet per second and an average density in the dense phase oi approximately 22 pounds per cubic foot is obtained. The dense phase provides even distribution oi gas flow and eiects suincient heat exchange with the waste gas.

The preheated reed powder is withdrawn from preheater 3 through-standplpe 0 at the rate of 95,000 pounds per hour. At the same time hot gas from reac r I' and economizer l is through line I into the bottom of carbonate reactor 2 at the rate of 67,585 pounds per hour and at a temperature oi approximately 1,600 F. That part or line II through which the resulting mixture o! powder and gas ilow to reactor 2 is dimensioned to provide a velocity oi' 50 feet per second. Carbonate reactorl has an inside diameter of 27 feet and provides a dense phase depth of approximately l5 feet. This occupies about one-hal! the volume of the carbonate reactor. In carbonate reactor 2 the reaction temperature oi 1,050 F. is maintained throughout by the introduction oi 5,886 pounds per hour of powdered coal. The oxygen necessary to support combustion is contained in the gas iitroduced through line II. The resulting intermediate product powder has a nlling weight oi approximately pounds per cubic i'oot whereby the average density oi.' the dense phase in carbonate reactor 2 is about 27 pounds per cubic foot. The average holding time for the powder in reactor 2 in accordance with the conditions outlined above is approximately 2.6 hours.

The product oi the combustion which takes place in the dense phase of the carbonate reactor, approximately '13,000 pounds per hour. together with the carbon dioxide liberated. approximately 34,000 pounds per hour, are discharged from carbonate reactor 2 through line l.

The powdered intermediate product is with- 40 drawn from reactor 2 through standpipe Il at the rate of approximately 61.221 pounds perphour (including 471 pounds per hour oi' ash). This powder is picked up inline Il by preheated air from economizer l which iiows through line I0 s at the rate oi 26,310 pounds per hour at 1,100' F.

That part oi' line I0 through which the resulting mixture passes is dimensioned to provide a linear velocity of 40 feet per second. Reactor I is dimensioned to provide an average holding time of approximately three houis. Consequently reactor I has an inner diameter of approximately i6 feet and the dense phase is maintained at a height o! approximately 27 feet. In order to maintain a reaction temperature of 'approximately 2,350 F. the heat or reaction must be supplemented. For this purpose 750 pounds oi' powdered coal per hour are charged to reactor Il in any suitable manner to maintain the reaction temperature at the desired level. The Iiuidised powder in reactor I has an average density in x the dense phase of approximately 36 pounds per cubic foot. r

The product powder is withdrawn from reactor I through standpipe 20 at the rate of apgg proximately 61,281 pounds per hour (including 531 pounds per hour of ash). This material is passed into line 23 at a temperature oi about 2,350 F. where it is picked up by air which is supplied by compressor 2l at the rate oi 66,895

perature o! 220 F.. and the product powder are contacted sumciently in economizer l to preheat the air to a temperature oi' 1,100 F. For this pul'DOse economizer l has an inside diameter of sponda to a maximum superiicial velocity of 14.5 and the fluid bed height is maintained at of approximately 25.4 pounds approximately 15 feet. The product powder, at a temperature of 1,100 F., is withdrawn through standpipe 25 at the rate of about 735 tons per day. The preheated air is divided at the top of economizer I to provide the volume of air required for reactor I', which flows through line I9, and the remainder is passed through line 25 to line II and into admixture with the hot gases from reactor I. This mixture has a temperature of about 1.600" F.

The foregoing operating conditions involve passing the gas streams through the various vessels at a maximum superficial velocity of 1.5 feet per second. Air is introduced through line 23 at a pressure of approximately 37 pounds gage at the exit of compressor 24. As a result of the pressure drop in line 23 the pressure is reduced to 30.5 pounds per square inch in the bottom of economizer l. The pressure drop caused by the dense bed in economizer 4 reduces the pressure The standpipes effect transfer of 9, I 5, 20 and 26 are provided to per square inch at the exit of valve I8. This corresponds to a powder density in standpipe I5 of about 35 pounds governed by the operating temperatures. Reac- `solid particles circulate at a 14 tors I and 2 are lined with suitablerei'ractory materials to withstand the relatively high temperatures existing in those zones of reaction and l it may be desirable also to provide such insulation for economizer 4. Preheater 3 may be con@ structed of sheet steel but considerable outside insulation is required for this vessel, and the others, to achieve maximum thermal eiiiciency in the system.

It may be desirable to replace valves Il and 22 with suitable ceramic lined throats having a xed interior dimension suitable for transferring solids at the desired rate. To adjust the rate of transfer of solids through such ilxed openings the density of the powder in the standpipe may be adjusted by varying the degree of aeration. This in turn regulates the pressure in the bottom of the standpipe.

In the production of a Portland cement it is necessary ordinarily to subject the product withdrawn through standpipe 26 to additional grinding to provide a powder of the requisite fineness.

I claim:

1. A method for oxide of a metal of producing a compound of an group II and at least one oxide `of a metal of groups III and IV which comprises nowing a gas stream upwardly in a reaction zone through a mass of finely divided solids containing said oxides to maintain the mass substantially in suspension in said stream. limiting the upward velocity of said gas stream to maintain the greater part of said mass of iinely divided solids in a relatively dense pseudo-liquid phase in which the high rate, maintaining said uidized mass of solids at a temperature high enough to produce the desired reactions, passing said gas stream out of said reaction Zone without substantial entrainment of said solids. cooling said gas stream outside said reactor to a temperature substantially lower than that of said reaction zone in a stepwise procedure comprising contacting said gas stream iirst with a second gas stream at a temperature substantially below the temperature of said reaction zone and then with a charge stream of said finely divided solids at a temperature substantially below the temperature of said second gas stream, treating said cooled gas stream to separate therefrom entrained solids, and returning said .separated solids to said reaction zone.

2. A method for producing a compound of an oxide of a metal of group II and at least one oxide of a metal of groups III and IV which comprises nowing a gas stream upwardly in a reaction zone through a mass of finely divided solids containing said oxides to maintain the mass substantially in suspension in said strea limiting the upward velocity of said gas stream to maintain the greater part of said mass of nely divided solids in a. relatively dense pseudo-liquid phase in which the solid particles circulate at a high rate, maintaining said fluidized mass of solids at a temperature high enough to produce the desired reactions, removing a part of said uidized mass of solids from said reaction zone independently of said gas stream. contacting said removed solids outside said reaction zone with a relatively cool gas stream to cool said solids and heat said gas stream, mixing at least a part of said heated gas stream with a preheated charge stream of said inely divided solids, and passing said mixture of gas and solids upwardly into said reaction none.

3. A method for producing a hydraulic cement which comprises flowing a gas stream upwardly ,divided sends which comprises flowing a in a reaction sone through a mass of nnely divided and calcium oxide to mainin suspension in said the upward velocity of said gas stream to maintain the greater part of -said mass solids in a relatively dense in which the solid particles ,and maintaining said fluidiaed a temperature substantially higher than 2000 F., withdrawing said gas stream from said first-mentioned reaction zone. introducing a mass oi finely divided solids containing calcium carbonate into said withdrawn gas stream and passing the mixture of gas and solids upwardly into a second reaction zone to to calcium oxide, solids comprising said second-mentioned iluidized mass including calcium oxide, and introducing the same into said gas stream prior to passage thereof upwardly in said first-mentioned reaction sone.

4. A method lor producing a hydraulic cement to maintain the mass substantially in suspension in said stream. limiting the upward velocity of said gas stream -to maintain the greater part of said mass of nnely divided solids in a relatively dense pseudo-liquid phase in which the solid particles circulate at a high rate. and maintaining said iluidlaed mass oi solids at a temperature substantially higher than 2000 F.. withdrawing said gas stream from said inst-mentioned reaction zone. introducing a mass oi finely divided solids containing withdrawn gas streamV and passing the mixture of gas and solids upwardly into a second reaction zone to maintain the mass in said second reaction sono in said dense nuidized condition, maintaining said last-mentioned fluidiaed mass of solids at a temperature substantially lower than 2000i F. but suiliciently high to convert said calcium carbonate to calcium oxide. and transferring a portion of the solids comprising said secondmentioned iluidized mass including calcium oxido to said mst-mentioned uidlzed mass by withdrawing a stream of said solids and introducing the same into said gas stream prior to its entry into said mst-mentioned reaction zone, passing said gas stream out of said second-mentioned reaction zone, cooling said withdrawn gas stream to a temperature not substantially higher than about i000 F., treating said cooled gas stream to separate therefrom entralned solids, and returning said separated solids to said secondmentioned reaction zone. f

5. A method for producing a hydraulic cement gas stream upwardly in a reaction sone through a mass of finely divided solids containing silica and calcium oxide to maintain the mass substantially in suspension in said stream, limiting the upward velocity oi said gas streamto maintain the greater part o! said mass oi iinely divided solids in a relatively dense pseudo-liquid phase in which the solid particles circulate at a high rate. and maintaining said fiuidized mass ci solids at a temperature substantially higher than2000 F., withdrawing said gas stream fromsaid mst-mentioned reaction none, introducing a mass calcium carbonate into said' ci aneiy divided 'N the mais in said ma 16 solids containing calcium carbonatinto said withdrawn gas streamand mixture oi.' gas and solids upwardly into a second reaction zone to maintain the mass in said second reaction zone in said dense nuidined condition, maintain- F.-but sumciently high to convert said calcium carbonate to calcium oxide, and transferring a portion of the solids comprising said secondmentioned iiuidized mass including 'cialcium oxide to said first-mentioned iimdized mass, removing a part oi said iiuidiaed mass of soiidsfrrom said mst-mentioned reaction sono, contacting said removed solids outside said first-mentioned reaction zone with a relatively cool gas stream to cool said solids and heat said gas stream. and nowing at least a part of said heated gas stream first-mentioned reaction sone portion of the solids transferred from said second-mentioned iluidized mass to said first-mentioned iluidined mass being admixed with said part oi.' said heated gas stream outside oi said reaction sones, and conveyed thereby into said inst-mentioned nuidized mass.

6. A method for producing a compound o! an oxide of a metal oi group II and at least one oxide of a metal of groups III and IV which comprises iiowing a gas stream upwardly in a reaction zone through a mass of nely divided solids containing said oxides to maintain the mass substantially in suspension in saidystream, limiting the upward velocity of said gas stream to maintain the greater part of said mass or finely divided solids in a relatively dense pseudo-liquid phase in which the solid: particles circulate at a high rate, maintaining said iiuidined mass of solids at a temperature high enough to produce the desired reactions, removing a part ci.' said nuidized mass of solids from said reaction sono independently of said gas stream, contacting said removed solids outside said reaction none with a relatively cool gas stream to cool said solids and heat said gas stream, mixing at least a part of said heated gas stream with a preheated charge stream o! said nnely divided solids maintained at a temperature substantially higher than the temperature o! said heated gas stream but below the temperature o: said reaction zone, and said mixture ci gas and solids upwardly into said reaction sono.

7. A method for producing a compound or an oxide of a metal oi group II and at least one oxide oi a metal of groups 111 and IV which comprises ilowing a gas stream at a velocity of 01` to 10 feet per second upwardly in a reaction zone through a mass of iinely divided solids containing said oxides to maintain the mass substantially in suspension in said stream, the greater part of said mass of nnely divided solids being maintained in the lower portion of said reaction zone in a relatively dense pseudo-liquid phase in which the solid particles circulate at a high rate and the remaining part of said mass being maintained in the upper portion o! said zone in a diusephase of considerably lower concentration of solids, maintaining said iiuidined mass o! solids at a temperature inthe range of about 2000 to 2850 F., withdrawing said gas stream from said iirstmentioned reaction sone, introducing a mass of nnely divided solids containing a carbonate oi a metal of group 1I into said withdrawn gas stream i mixture of gas and solids upwardly into a second reacidon sone to maintain rewtin non@ in said i7 dense iiuidized condition. maintaining said lastmentioned iiuidized mass of solids atea temperature substantially lower than the temperature maintained in said first-mentioned nuidized mass but sumciently high to convert said metal carbonate to the corresponding .metal oxide, and transferring a portion of the solids comprising said second-mentioned uidized mass including said last-mentioned metal oxide to said rstmentloned uidized mass. l 8. A method for producing a compound oi an ,oxide of a metal of group 1I and at least one oxide o! a me.il of groups III and IV which comprises iiowing a gas stream at a velocity of 0.1 to i feet per second upwardly in a reaction zone through a mass oi finely divided solids containing said oxides to maintain the mass substantially in suspension in said stream, the greater part of said mass of iinely divided solids being maintained in the lower portion of said reaction zone in a relatively dense pseudo-liquid phase in which the `solid particles circulate at a high rate and the remaining part of said mass being maintained in the upper portion of said zone in a diffuse phase oi considerably lower concentration of solids, maintaining said tluidized mass of solids at a temperature in the range of about 2000 to 2650n F., withdrawing said gas stream from said firstmentioned reaction zone, introducing a mass oi iinely divided solids containing a carbonate of a metal of group II into said withdrawn gas stream and passing the mixture of gas and solids upwardly in a second reaction 4zone to maintain the mass in said second reaction zone in said dense fluidized condition, maintaining said lastmentioned iiuldized mass of solids at a temperaturc substantially lower than the temperature maintained in said first-mentioned uidized mass but suiliciently high to convert said metal carbonate to the corresponding metal oxide, withdrawing a portion of the solids comprising said second-mentioned fiuidized mass including said last-mentioned metal oxide and introducing the same into said gas stream prior to its entry into said first-mentioned reaction zone.

9. A method for producing a compound of an oxide of a metal of group II and at least one oxide oi' a metal of groups III and IV which comprises iiowing a gas stream upwardly in a reaction zone through a mass of finely divided solids containing said oxides to maintain the mass substantially in suspension in said stream, limiting the upward velocity of said gas stream to maintain the greater part of said mass of nely divided solids in a relatively dense pseudo-liquid phase in which the solid particles circulate at a high rate, maintaining said iluidized mass of solids at a temperature in the range of about 2000 to 2650 F., withdrawing said gas stream from said first-mentioned reaction zone, introducing a mass of nely divided solids containing a carbonate of a metal of group II into said withdrawn gas stream and then passing the mixture of gas and solids into a second reaction zone, wherein the mass in maintained in said dense uidlzed condition, maintaining said last-mentioned iluidized mass oi solids 'at a temperature substantially lower than the temperature maintained in said first-mentioned fluidlzed mass but suiliciently high to convert said metal carbonate to the corresponding metal oxide, removing a part of the iiuidized mass of solids from said first-mentioned reaction zone, contacting said removed solids outside 'said reaction zone with a relatively cool gas stream to cool said solids and heat said stream, withdrawing a portion of -18 the solids comprising said second-mentioned iiuidized mass including said last-mentioned metal oxide and introducing the same into a part of said last-mentioned heated gas stream, passing said solids with said gas stream upwardly into said mst-mentioned reaction zone as described. and combining another part of said lastmentioned heated gas stream with said gas stream emerging from said first-mentioned reaction mile prior to passage thereof into said second-mentioned reaction zone as 10. A method as in claim 5 in which said iiuldized solids removed from said mst-mentioned reaction zone are introduced into said cool. gas stream and are then conveyed thereby upwardly into a cooling lzone wherein said solids comprising said hydraulic cement are cooled while being maintained as a mass in said dense iiuidized condition.

li. A method for producing a hydraulic cement comprising the steps of passing a mass o! nely divided solids containing sili'ca and calcium carbonate stage-wise `through a series oi zones including, in order, a preheating zone a calcinlng zone wherein said calcium carbonate is converted to the oxide, a reaction zone wherein the desired reaction is carried out, and a cooling zone, countercurrent to a stream of gas nowing stage-wise through said series of zones in reverse order, said gas stream passing upwardly in each zone through a mass of said finely divided solids at a velocity suitable to maintain the greater part of said mass suspended in said gas stream in a relatively dense pseudo-liquid phase, the ilnely divided solids prior to their entry into each of said preheating, ealcining and reaction zones being introduced into the gas stream discharging from the next following zone, and the finely divided solids prior to entry into said cooling zone being introduced into the feed stream of said gas, said gas streams conveying said solids upwardly into said zones. l

l2. A method for producing a compound of an oxide of a metal of group II and at least one oxide of a metal of groups III and IV which comprises the steps oi passing a mass oi ilnely divided solids containing at least one oxide of a metal of groups III and IV and a carbonate oi a metal of group lI stage-wise through a series of zones including. in order, a preheating zone. a reaction zone wherein said carbonate is converted to the corresponding oxide, a second reaction zone wherein the desired reaction is carried out, and a cooling zone, countercurrent to a stream of gas flowing stage-wise through said series of zones in reverse order, said gas stream passing upwardly in each zone through a mass of said iinely divided solids at a velocity suitable to maintain the greater part of said mass suspended in said gas stream in a relatively dense pseudo-liquid phase, the nely divided solids prior to .their entry into each of said preheating. caicining and reaction zones being introduced into the gas stream discharging from the next i'ollowing zone. and the nely divided solids prior to entry into said cooling zone being introduced into the feed stream of said gas. said gas streams conveying said solids into said zones.`

13. A method as in claim 12 in which said zones are maintained at progressively increasing pressures in the order recited, and the solids prior to their introduction into the gas stream entering each zone are passed downwardly in an elongated confined path to increase the static memes Dxessure therein sumcientiy to effect the injection of said solids into said gas stream.

14. A method asin claim 13 in which said elongated eonnned paths are constricted at their discharge ends to provide predetermined fixed rates of solids discharge.

15. A method as in claim 14 including the steps of iniecting aerating sas into said elongated confined paths and adjustingv the ow of aerating gas into each of said paths to produce a solids concentration therein suitable to provide a. desired rate of solids discharge through said constrictions.

ROBERT PYZEL.

20 REFERENCES crrEn The following references are of record in the file of this patent:

UNITED STATES PATENTE Number Name Date 371,715 Sonnet Oct. 18, 1887 1,536,702 Chase May 5, 1925 1,557,873 Pike Oct. 20, 1925 1,746,294 Tyler Feb. 11, 1930 1,828,270 Y Anderson Oct. 20, 1931 2,300,042 Caldwell Oct. 27, `1942 2,409,707 Roetheli Oct. 22, 1916 

